Dipyrrolyl‐Functionalized Bipyridine‐Based Anion Receptors for Emission‐Based Selective Detection of Dihydrogen Phosphate

New cationic anion receptors, based on the use of pyrrole-substituted bipyridine and coordinated to transition metals, are described. Specifically, polypyridine-ruthenium and -rhodium cores have been functionalized to generate an anion binding site. The design was chosen to probe the influence of the pyrrole-to-pyrrole separation on anion-binding affinities and selectivities; this distance is greater in the new systems of this report (receptors 1 and 2) relative to that present in related dipyrrolyl quinoxaline based receptors 3 and 4. Solution-phase anion-binding studies, carried out by means of (1)H NMR spectroscopic titrations in [D(6)]DMSO and isothermal titration calorimetry (ITC) in DMSO, reveal that 1 and 2 bind most simple anions with substantially higher affinity than either 3 or 4. In the case of chloride anion, structural studies, carried out by means of single-crystal X-ray diffraction analyses, are consistent with the solution-phase results and reveal that receptors 1 and 2 are both able to stabilize complexes with this halide anion in the solid state.